Dielectric ceramic composition, shaped body and electronic component

Abstract

A dielectric ceramic composition which is a dielectric ceramic composition containing forsterite as a main component and containing a glass component as a subcomponent, wherein the glass component contains lithium, calcium, barium, and silicon, and the glass component is added in an amount of 12 parts by weight or more with respect to 100 parts by weight of the main component.

Description

Technical Field

[0001] This disclosure relates to dielectric ceramic compositions, molded bodies, and electronic components using the same. Background Technology

[0002] A device with high-frequency circuitry is known. This device is, for example, a mobile phone. The high-frequency circuitry includes a filter. A dielectric filter is widely used as this filter. The dielectric filter is a filter that uses a stacked dielectric ceramic. For this dielectric ceramic, it is required that it can be appropriately used in high-frequency bands of several GHz.

[0003] A method for manufacturing a dielectric filter includes steps described below. First, a conductive paste is applied to multiple molded bodies made of ceramic powder constituting the dielectric. Electrode patterns (conductive paste layers) are formed using the applied conductive paste. Next, the multiple molded bodies with the electrode patterns are stacked to form a laminate, which is then fired. This process densifies the conductive paste layer and the multiple molded bodies by simultaneous firing. In this manufacturing method, the sintering temperature of the molded bodies needs to be lower than the melting point of the conductive material (metallic material) contained in the conductive paste. Summary of the Invention

[0004] Dielectric ceramic compositions with better properties are desired.

[0005] The purpose of this invention is to solve the above-mentioned problems.

[0006] The first aspect of the present invention is a dielectric ceramic composition containing magnesium olivine as a main component and a glass component as a secondary component, wherein the glass component comprises lithium, calcium, barium, and silicon, and 12 or more parts by weight of the glass component are added relative to 100 parts by weight of the main component.

[0007] A second aspect of the present invention is a molded body having the above-described dielectric ceramic composition.

[0008] The third aspect of the present invention is an electronic component having the above-described molded body.

[0009] According to the present invention, a dielectric ceramic composition with better properties can be provided.

[0010] Brief description of the attached diagram Figure 1 This is a side view showing a portion of the side of an electronic component in one embodiment.

[0011] Figure 2 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0012] Figure 3It is a graph showing the relationship between the amount of glass added and the fQ value based on Examples 1-8 and Comparative Examples 1-5.

[0013] Figure 4 It is a graph showing the relationship between the amount of glass added and the strength based on Examples 1-8 and Comparative Examples 1-5.

[0014] Figure 5 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0015] Figure 6 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0016] Figure 7 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0017] Figure 8 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0018] Figure 9 This is a table representing the experimental results of multiple embodiments.

[0019] Figure 10 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0020] Figure 11 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0021] Figure 12 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0022] Figure 13 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0023] Figure 14 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples.

[0024] Figure 15 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Detailed Implementation

[0025] Japanese Patent Application Publication No. 2000-211969 discloses ceramics (dielectric ceramics) incorporating various types of glass in the Ba-Al-Si-O system. According to this publication, the sintering temperature of the ceramic is below 1000°C, which is relatively low. However, the flexural strength of the ceramic disclosed in this publication is below 270 MPa, making it unsuitable for applications requiring high strength substrates.

[0026] Furthermore, according to Japanese Patent Application Publication Nos. 2021-155235 and 2006-335633, by adjusting the composition of forsterite (Mg2SiO4) as the main component, the secondary component, and the glass as an additive, dielectric ceramic compositions with relatively high Q values ​​and flexural strength can be obtained. However, the dielectric constant of the dielectric ceramic compositions disclosed in Japanese Patent Application Publication Nos. 2021-155235 and 2006-335633 increases due to the presence of additives (glass) in the dielectric ceramic compositions, exceeding 9.

[0027] Based on the above preliminary description, one implementation method will be described below.

[0028] It should be noted that the “dielectric constant” (relative dielectric constant, εr) in the following description is determined using test pieces formed from sintered bodies of the dielectric ceramic composition described later. The dielectric constant is determined by the two-terminal short-circuit dielectric resonator method based on the “Test Method for Dielectric Properties of Microwave Fine Ceramics” (JIS-R-1627).

[0029] The “fQ value” in the following description is derived based on the dielectric loss tangent (tanδ) of the test piece obtained by the above-described short-circuit dielectric resonator method, using the aforementioned test piece as the test object. More specifically, the product of the reciprocal of the dielectric loss tangent of the test piece, i.e., the Q value (quality coefficient), and the resonant frequency of the test piece (unit: GHz) is used as the fQ value of the test piece.

[0030] The “temperature characteristic” (Tf) in the following description can be expressed as the rate of change (ppm / °C) of the resonant frequency of the dielectric ceramic composition due to temperature changes. The temperature characteristic is derived based on the change in the resonant frequency of the test piece obtained by the above-described short-circuit dielectric resonator method, using the test piece as the test object. The temperature change is based on 20°C and ranges from 0°C to 85°C.

[0031] The "strength" described below is determined as follows: a laminate (test piece) is formed by stacking multiple ceramic sheets, which are sintered from a dielectric ceramic composition, and a three-point bending strength test is performed on the test piece. For this three-point bending strength test, the test piece size is set to 30 mm × 2.0 mm. The "acid resistance" described below is evaluated as follows: the test piece, which has been immersed in two acidic solutions for 3 hours each, is cross-section-ground, and the erosion distance of the ground surface is measured. The evaluation is based on this erosion distance. The test piece used for acid resistance is a laminate (thickness 0.6 mm, length 1.6 mm, width 0.8 mm) of multiple ceramic sheets, formed from a sintered dielectric ceramic composition. One of the two acidic solutions is an acidic solution with nickel sulfamate as the main component (temperature 55°C, pH 4.5). The other of the two acidic solutions is an acidic solution with tin methanesulfonate as the main component (temperature 35°C, pH 4.5). The erosion distance is measured using a scanning electron microscope.

[0032] (One implementation method) Figure 1 This is a side view showing a portion of the side of an electronic component 10 according to one embodiment.

[0033] Electronic component 10 is, for example, a filter. It should be noted that for more detailed configuration of the filter, please refer, for example, to Japanese Patent Application Publication No. 2023-125226. Furthermore, electronic component 10 is not limited to a filter. Electronic component 10 can also be, for example, a capacitor. Figure 1 As shown, the electronic component (electronic device) 10 has multiple sintered bodies 14 and conductors 12. The multiple sintered bodies 14 are stacked. It should be noted that in Figure 1 The diagram shows three stacked sintered bodies 14, but more than one sintered body 14 (not shown) is further stacked on top of these three sintered bodies 14. The sintered body 14 is a molded body 16 of the sintered dielectric ceramic composition. That is, the sintered body 14 can be obtained by sintering the molded body 16 obtained by molding the dielectric ceramic composition of this embodiment. A more detailed description of the dielectric ceramic composition will be given later. The electronic component 10 can be manufactured, for example, by integrally firing the molded body 16 and the conductor 12. More specifically, in the molded body 16 containing ceramic powder formed from the dielectric ceramic composition, an opening for embedding the conductor 12 is formed by laser processing, and after embedding the paste-like conductor 12 in the opening, firing is performed. Thus, the electronic component 10 can be manufactured. The conductor 12 may include a through-hole electrode 121 and a flat electrode 122, but is not limited thereto.

[0034] As described above, the dielectric ceramic composition can be used as a material for electronic component 10. The dielectric ceramic composition is, for example, a powder (powder). The dielectric ceramic composition contains a main component and secondary components.

[0035] The main component contains magnesium olivine (Mg2SiO4). The main component may also contain at least one of barium titanate (BaTiO3), strontium titanate (SrTiO3), and calcium titanate (CaTiO3). This improves the temperature characteristics of the dielectric ceramic composition.

[0036] However, if the content of barium titanate in the main component is too high, the fQ value of the dielectric ceramic composition will decrease excessively. Therefore, the content of barium titanate in the main component is preferably 7 mol% or less. This helps to suppress the excessive decrease in the fQ value.

[0037] Furthermore, if the content of strontium titanate in the main component is too high, the dielectric constant of the dielectric ceramic composition will increase excessively. Therefore, the content of strontium titanate in the main component is preferably 13 mol% or less. This helps to suppress the excessive increase in the dielectric constant.

[0038] Similarly, if the content of calcium titanate in the main component is too high, the dielectric constant of the dielectric ceramic composition will increase excessively. Therefore, the content of calcium titanate in the main component is preferably 17 mol% or less. This helps to suppress the excessive increase in the dielectric constant.

[0039] The secondary components include a glass component (glass). The glass component is added to the main component as an additive. The glass component comprises a first glass component and a second glass component, as described below.

[0040] The first glass component of this embodiment contains lithium (Li). In the following description, the lithium content in the first glass component is also referred to as the Li content. The Li content can be expressed as the content of lithium oxide (Li₂O) converted from the lithium content in the first glass component. The Li content is 6 wt% or more and 18 wt% or less.

[0041] When the Li content is too low, the various components in the glass composition will not melt, and a uniformly shaped glass body may not be obtained. In other words, a low Li content increases the likelihood of not obtaining a good glass body. In this respect, by ensuring the Li content is 6 wt% or higher, a good glass body is easily obtained. Furthermore, by ensuring the Li content is 6 wt% or higher, the sintering temperature of the dielectric ceramic composition can be easily suppressed to below 950°C. Therefore, when manufacturing an electronic component 10 having a dielectric ceramic composition and a conductor 12 by firing, silver can be used as the conductor 12. That is, the melting point of silver is approximately 960°C. If the sintering temperature of the dielectric ceramic composition is higher than 960°C, silver will melt during sintering, making it difficult to manufacture an electronic component 10 with silver as the conductor 12. In this respect, according to this embodiment, the dielectric ceramic composition can be sintered without melting silver. Copper can also be used as the conductor 12. The melting point of copper is approximately 1085°C. Therefore, by suppressing the sintering temperature of the dielectric ceramic composition to below 950°C, when manufacturing an electronic component 10 having copper as a conductor 12 by firing, the dielectric ceramic composition can be sintered without melting the copper. It should be noted that, as described above, the sintering temperature of the dielectric ceramic composition is preferably below 950°C, more preferably below 920°C. When the sintering temperature of the dielectric ceramic composition is below 920°C, the possibility of melting of silver, copper, etc., is further reduced.

[0042] By keeping the Li content below 18 wt%, a sintered body 14 with a good fQ value can be obtained. It should be noted that, in this embodiment, a good fQ value is defined as 15000 or higher.

[0043] The first glass composition contains calcium (Ca). In the following description, the calcium content in the first glass composition is also referred to as the Ca content. The Ca content can be expressed as the content of calcium oxide (CaO) converted from the calcium content in the first glass composition. The Ca content is 2 wt% or more and 9 wt% or less. By making the Ca content 2 wt% or more, the decrease in the fQ value can be suppressed. By making the Ca content 9 wt% or less, the increase in the dielectric constant of the sintered body 14 can be suppressed. It should be noted that the standard for a desirable dielectric constant in this embodiment is 9.0 or less. The lower the dielectric constant of the sintered body 14, the more preferred. For example, the dielectric constant of the sintered body 14 is further preferably 8.5 or less.

[0044] The first glass composition contains barium (Ba). In the following description, the barium content in the first glass composition is also referred to as the Ba content. The Ba content can be expressed as the content of barium oxide (BaO) converted from the barium content in the first glass composition. The Ba content is 6 wt% or more and 20 wt% or less. By ensuring the Ba content is 6 wt% or more, the decrease in the fQ value can be suppressed. By ensuring the Ba content is 20 wt% or less, the increase in the dielectric constant can be suppressed.

[0045] The first glass composition may also contain strontium (Sr). The first glass composition may also not contain strontium. In the following description, the strontium content in the first glass composition is also referred to as the Sr content. The Sr content can be expressed as the content of strontium oxide (SrO) converted from the strontium content in the first glass composition. The Sr content is 0 wt% or more and 7 wt% or less. By keeping the Sr content at 7 wt% or less, the increase in dielectric constant can be suppressed.

[0046] The first glass composition contains silicon (Si). In the following description, the silicon content in the first glass composition is also referred to as the Si content. The Si content can be expressed as the content of silicon dioxide (SiO2) converted from the silicon content in the first glass composition. The Si content is 50 wt% or more and 75 wt% or less. The silicon composition is the remainder of the glass composition after removing lithium, calcium, barium, and strontium. This remainder can be entirely composed of silicon, but is not limited to this. For example, the glass composition may also contain less than 1 wt% alumina (Al2O3). It should be noted that if the Si content is too high, the various components in the glass composition may not melt, potentially resulting in an overall non-uniform glass body. That is, if the Si content is too high, the likelihood of not obtaining a good glass body is relatively high. In this respect, by keeping the Si content to 75 wt% or less, it is easier to obtain a good glass body.

[0047] Calcium (Ca), barium (Ba), and strontium (Sr) belong to the alkaline earth group (alkaline earth elements). Hereinafter, the total content of alkaline earth compounds in the glass composition is also referred to as the total alkaline earth group content. That is, in this embodiment, the total alkaline earth group content is the sum of the aforementioned Ca, Ba, and Sr contents. The total alkaline earth group content affects the change in dielectric constant. The change in dielectric constant is the increase in dielectric constant corresponding to a 1-part increase in the amount of glass composition added. The greater the increase in the total alkaline earth group content, the greater the rate of increase in dielectric constant. By adjusting the total alkaline earth group content, the rate of increase in dielectric constant can be adjusted. That is, by suppressing the change in dielectric constant, the increase in dielectric constant can be suppressed. The total alkaline earth group content is preferably 32 wt% or less. More preferably, it is 25 wt% or less. More preferably, it is 22 wt% or less. More preferably, it is 19 wt% or less. More preferably, it is 11 wt% or less.

[0048] The second glass component includes boron-based glass. Therefore, the sintering temperature of the molded body 16 (dielectric ceramic composition) can be lowered. The content of the second glass component in the dielectric ceramic composition is 3 parts by weight or less relative to 100 parts by weight of the main component. This suppresses the degradation of the acid resistance of the dielectric ceramic composition due to the presence of boron-based glass. The second glass component may also be omitted from the dielectric ceramic composition. When the dielectric ceramic composition contains a second glass component, the content of the second glass component relative to 100 parts by weight of the main component is more preferably 2 parts by weight or less. This further suppresses the degradation of the acid resistance of the dielectric ceramic composition due to the presence of boron-based glass. It should be noted that, as described above, acid resistance is evaluated based on the aforementioned erosion distance. The permissible standard for the erosion distance in this embodiment is 3 μm or less.

[0049] The aforementioned glass component is added at a content of 12 parts by weight or more and 25 parts by weight or less relative to 100 parts by weight of the main component. For example, when the content of the second glass component is 2 parts by weight relative to 100 parts by weight of the main component, the content of the first glass component is 10 parts by weight or more and 23 parts by weight relative to 100 parts by weight of the main component. By making the amount of glass component added 12 parts by weight or more relative to 100 parts by weight of the main component, a sintered body 14 with sufficient strength can be obtained. It should be noted that the standard for sufficient strength in this embodiment is 270 MPa or more. The content of the second glass component can be appropriately adjusted within the range where the dielectric constant of the sintered body 14 is 9.0 or less and the strength of the sintered body 14 is 270 MPa or more.

[0050] By keeping the amount of glass component added at 25 parts by weight or less relative to 100 parts by weight of the main component, the decrease in the fQ value of the sintered body 14 and the deterioration of the temperature characteristics of the sintered body 14 can be suppressed. It should be noted that in this embodiment, a temperature characteristic is considered good if the absolute value of the temperature characteristic of the sintered body 14 is 60 ppm / °C or less. More preferably, the absolute value of the temperature characteristic of the sintered body 14 is 30 ppm / °C or less.

[0051] The dielectric ceramic composition may also contain copper compounds. Examples of copper compounds include copper oxide (CuO), but it is not limited to this. For instance, copper compounds may also be carbonates, nitrates, oxalates, hydroxides, sulfides, organometallic compounds, etc.

[0052] When a copper compound is contained in a dielectric ceramic composition, the copper compound is contained in an amount greater than 0 parts by weight and less than 7 parts by weight (calculated as copper oxide, CuO) relative to 100 parts by weight of the main component. The presence of a copper compound in the dielectric ceramic composition can lower its sintering temperature. By ensuring that the copper compound content in the dielectric ceramic composition is less than 7 parts by weight (calculated as copper oxide), the decrease in the fQ value can be suppressed.

[0053] The sintered body 14 (molded body 16 of dielectric ceramic composition) described above is manufactured, for example, based on the manufacturing method described below. This manufacturing method includes a first step, a second step, a third step, and a fourth step.

[0054] In the first step (main component preparation step), the main component is prepared. More specifically, the main component is prepared according to the following steps (1) to (3). (1) Prepare Mg oxide and Si oxide as starting materials. It should be noted that the starting materials may also be compounds that can be heat-treated to obtain Mg oxide and Si oxide. (2) Prepare a mixed powder in which the starting materials are mixed. Hereinafter, this mixed powder is referred to as the first mixed powder. The first mixed powder is obtained by wet pulverizing the starting materials. The molar ratio of Mg element to Si element in the first mixed powder is set to 2:1. (3) Calcine the first mixed powder and pulverize the calcined first mixed powder. Thus, the main component powder is obtained. The main component powder is the powder of the main component (magnesium olivine). It should be noted that the first mixed powder is calcined at 1000°C to 1200°C for 2 to 3 hours, but is not limited to this.

[0055] In the first process, the operation of obtaining powders of barium titanate, strontium titanate, and calcium titanate may be appropriately included. By appropriately changing the above-mentioned starting materials to calcium carbonate, barium carbonate, strontium carbonate carbonate, titanium oxide, etc., powders of barium titanate, strontium titanate, and calcium titanate can be obtained. The powders of barium titanate, strontium titanate, and calcium titanate are included in the main component powder together with the above-mentioned forsterite powder. In this case, the molar ratio of Ba to Ti is 1:1. The molar ratios of Sr to Ti and Ca to Ti are also 1:1.

[0056] In the second process (sub-component preparation process), a glass component (first glass component) is prepared as a sub-component. More specifically, the glass component is prepared according to the following steps (4) to (7). (4) SiO2, Li2CO3, CaCO3, BaCO3 and SrCO3 are mixed in the desired amounts to obtain a mixed powder. Hereinafter, this mixed powder is referred to as the second mixed powder. (5) The second mixed powder is heated to melt it and then cooled to obtain a glass molded body. Heating is performed using, for example, heat of 1200°C to 1500°C. (6) The glass molded body is crushed and then graded. (7) The graded glass molded body (powder) is crushed. Thus, a sub-component powder is obtained. The sub-component powder is the powder of the sub-component (glass component). It should be noted that the material mixed in (4) above may also be a compound that can be obtained by heat treatment to obtain SiO2, Li2O, CaO, BaO and SrO. In the second process, the above-mentioned second glass component may also be further prepared as an additional sub-component. For example, the second glass composition is prepared according to the following steps (A) to (D). (A) SiO2, BaCO3, B2O3, and ZnO are mixed in the desired amounts to obtain a mixed powder. (B) The obtained mixed powder is heated to melt it and then cooled to obtain a glass molded body. Heating is performed using, for example, heat of 1200°C to 1500°C. (C) The obtained glass molded body is pulverized and then graded. (D) The graded glass molded body (powder) is pulverized. Thus, a boron-based glass (second glass composition) powder containing SiO2, BaO, B2O3, and ZnO is obtained. It should be noted that the materials mixed in (A) above can also be compounds that can be heat-treated to obtain SiO2, BaO, B2O3, and ZnO.

[0057] In the third step (sample manufacturing step), the secondary component powder obtained in the second step is added to the main component powder obtained in the first step. This yields the dielectric ceramic composition powder of this embodiment. The glass component is added at a content of 12 parts by weight or more and 25 parts by weight or less relative to 100 parts by weight of the main component. Hereinafter, the obtained dielectric ceramic composition powder will be referred to as sample powder. The sample powder may also contain a copper compound (powder).

[0058] In the fourth step (sintering step), the sample powder is sintered to obtain a sintered body 14 of the dielectric ceramic composition. More specifically, the sample powder is sintered according to the following steps (8) to (11). (8) While adding a molding aid to the sample powder, it is shaped into a sheet using a prescribed molding method. Thus, a ceramic sheet is obtained. The molding aid is, for example, an organic binder. The prescribed molding method is, for example, compression molding, scraping, etc. (9) Multiple ceramic sheets are stacked to form a laminate. The laminate may also be subjected to compression processing. (10) The laminate is cut according to the desired size to obtain a molded body 16 of the dielectric ceramic composition. (11) The molded body 16 is fired to obtain a sintered body 14. The molded body 16 is heated for 2 hours using, for example, a temperature of 850°C to 950°C. Example

[0059] Hereinafter, the characteristics of the dielectric ceramic composition of one embodiment will be described by comparing examples with comparative examples.

[0060] Figure 2 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 2 Examples 1-8 and Comparative Examples 1-5 are shown in the figure.

[0061] Figure 2 The "Main Components" column indicates the main components of the dielectric ceramic composition. Figure 2 The "Glass Composition" column indicates the content (wt%) of various components in the glass. More specifically, Figure 2 The "SiO2" column indicates the Si content mentioned above. Figure 2 The "Li2O" column indicates the Li content mentioned above. Figure 2 The “BaO” column indicates the Ba content mentioned above. Figure 2 The "CaO" column indicates the Ca content mentioned above. Figure 2 The "SrO" column indicates the Sr content mentioned above. Figure 2 The “Glass Addition Amount” column indicates the amount of glass component added (parts by weight) relative to 100 parts by weight of the main component. Figure 2 The "Vitrification" column indicates whether a good glass molded body was obtained in the second process described above. "OK" in the "Vitrification" column indicates a good glass molded body was obtained. "NG" in the "Vitrification" column indicates that a good glass molded body was not obtained. That is, "NG" in the "Vitrification" column indicates that in step (7) of the second process described above, the various components in the glass composition did not melt, and a uniformly shaped glass molded body could not be obtained. Figure 2 The “Sintering Temperature” column indicates the temperature at which the laminate is sintered in the fourth process described above.

[0062] exist Figure 2 The "Characteristics" section displays the various characteristics (εr, fQ value, Tf, strength) measured using the methods described above. εr (dielectric constant), fQ value, and Tf (temperature characteristic) were measured using a test piece (sintered body) with a diameter of 16 mm and a height of 8 mm. For a test piece (sintered body) with a longitudinal dimension of 30 mm, a transverse dimension of 2.0 mm, and a height of 1.8 mm, 30 strength measurements were performed, and the average of the 30 strength measurements (three-point bending strength) was recorded as the strength of the test piece.

[0063] Figure 3 It is a graph showing the relationship between the amount of glass added and the fQ value based on Examples 1-8 and Comparative Examples 1-5. Figure 4 This is a graph showing the relationship between the amount of glass added and the strength, based on Examples 1-8 and Comparative Examples 1-5. It should be noted that, due to the limitation of the vertical axis range of the graph, [the following is omitted]. Figure 3 , Figure 4 The numerical values ​​of Comparative Example 1 are plotted.

[0064] In Examples 1-8 and Comparative Examples 1-5, the glass composition was the same, but the amount of glass added was different. In Examples 1-8, the amount of glass component added relative to 100 parts by weight of the main component was controlled within a range of 12 parts by weight or more and 25 parts by weight or less, but in Comparative Examples 1-5, the amount of glass component added was outside this range. As a result, such as Figures 2-4 As shown, in Examples 1-8, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all good. In contrast, in Comparative Examples 1-5, at least one of the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength was not within the good range. For example, in Comparative Example 4, the fQ value did not reach 15000. Furthermore, for example, in Comparative Example 4, the absolute value of the temperature characteristic exceeded 60.

[0065] according to Figures 2-4 It can be confirmed that even with a fixed glass composition, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength vary depending on the amount of glass added. Furthermore, according to... Figures 2-4 It can be confirmed that if the amount of glass added is in the range of 12 parts by weight or more and 25 parts by weight or less relative to 100 parts by weight of the main component, a good dielectric ceramic composition can be easily obtained.

[0066] Figure 5 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 5 Examples 9-12 and Comparative Examples 6-9 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 5 Further details are shown in the middle.

[0067] Figure 5 The "Alkaline Earth Group Composition" column is shown. As mentioned above, the alkaline earth group composition is the total amount of alkaline earth compounds contained in the glass composition. That is, in Figure 5 The “Alkaline Earth Group Total Measurement” column shows the total (wt%) of the Ca content shown in the “CaO” column, the Ba content shown in the “BaO” column, and the Sr content shown in the “SrO” column. Figure 5 The information shown in the other columns is according to Figure 2 .

[0068] In Examples 9-12 and Comparative Examples 6-9, the amount of glass added was the same, but the Li content was different. In Examples 9-12, the Li content was controlled within the range of 6 wt% to 18 wt%, but in Comparative Examples 6-9, the Li content was outside this range. As a result, as Figure 5 As shown, in Examples 9-12, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all excellent. In contrast, in Comparative Examples 6 and 7, which had a lower Li content, the byproducts did not vitrify well, and the sintering temperature exceeded 1000°C. Furthermore, in Comparative Examples 6 and 7, the absolute values ​​of the temperature characteristics exceeded 60. In Comparative Examples 8 and 9, which had a higher Li content, the fQ value did not reach 15000.

[0069] according to Figure 5 It can be confirmed that even with a fixed amount of glass added, the sintering temperature and fQ value vary considerably depending on the Li content. Furthermore, according to... Figure 5 It can be confirmed that a good dielectric ceramic composition can be obtained if the Li content in the glass composition is above 6 wt% and below 18 wt%.

[0070] Figure 6 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 6 Examples 13-16 and Comparative Examples 10 and 11 are shown. Additionally, for comparison, Figure 2 Also shown in Embodiment 3 Figure 6 Further details are shown in the middle. Figure 6 The table format is in accordance with Figure 5 .

[0071] In Examples 13-16 and Comparative Examples 10 and 11, the amount of glass added was the same, but the Ca content was different. In Examples 13-16, the Ca content was controlled within the range of 2 wt% to 9 wt%, but in Comparative Examples 10 and 11, the Ca content was outside this range. As a result, as Figure 6As shown, in Examples 13-16, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all excellent. In contrast, in Comparative Example 10, which had a lower Ca content, the fQ value did not reach 15000. Furthermore, in Comparative Example 11, which had a higher Ca content, the dielectric constant exceeded 9.0.

[0072] according to Figure 6 It can be confirmed that even with a constant glass addition, the fQ value and dielectric constant vary considerably depending on the Ca content. Furthermore, according to... Figure 6 It can be confirmed that a good dielectric ceramic composition can be obtained if the Ca content is above 2wt% and below 9wt%.

[0073] Figure 7 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 7 Examples 17-23 and Comparative Examples 12-15 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 7 Further details are shown in the middle. Figure 7 The table format is in accordance with Figure 5 .

[0074] In Examples 17-23 and Comparative Examples 12-15, the amount of glass added was the same, but the Ba content was different. In Examples 17-23, the Ba content was controlled within the range of 6 wt% to 20 wt%, but in Comparative Examples 12-15, the Ba content was outside this range. As a result, as Figure 7 As shown, in Examples 17-23, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all excellent. In contrast, in Comparative Examples 12-14, which had a lower Ba content, the fQ value did not reach 15000. Furthermore, in Comparative Examples 12 and 13, the byproducts did not vitrify well. In addition, in Comparative Example 15, which had a higher Ba content, the dielectric constant exceeded 9.0.

[0075] according to Figure 7 It can be confirmed that even with a fixed amount of glass added, the fQ value and dielectric constant will vary considerably depending on the Ba content. Furthermore, according to... Figure 7 It can be confirmed that a good dielectric ceramic composition is easily obtained if the Ba content is above 6 wt% and below 20 wt%.

[0076] Figure 8 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 8 Examples 24-29 and Comparative Examples 16-18 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 8Further details are shown in the middle. Figure 8 The table format is in accordance with Figure 5 .

[0077] In Examples 3, 24-27, and Comparative Example 16, the amount of glass added was the same, but the Sr content was different. In Examples 3 and 24-27, the Sr content was controlled within a range of 0 wt% to 7 wt%, but in Comparative Example 16, the Sr content was outside this range. As a result, as Figure 8 As shown, in Examples 3 and 24-27, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all good. In contrast, in Comparative Example 16, the dielectric constant exceeded 9.0.

[0078] according to Figure 8 It can be confirmed that even with a fixed amount of glass added, the dielectric constant varies considerably depending on the Sr content. Furthermore, according to... Figure 8 It can be confirmed that a good dielectric ceramic composition can be obtained if the Sr content is above 0 wt% and below 7 wt%.

[0079] In addition, such as Figure 8 As shown, it can be confirmed that good dielectric ceramic compositions were also obtained in Examples 28 and 29. In contrast, it can be confirmed that good dielectric ceramic compositions were not obtained in Comparative Examples 17 and 18. For example, in Comparative Example 17, the by-components did not vitrify well, and the sintering temperature reached 1000°C. In Comparative Example 18, the dielectric constant exceeded 9.0.

[0080] Figure 9 This is a table representing the experimental results of multiple embodiments. Figure 9 Examples 30 to 34 are shown in the figure.

[0081] exist Figure 9 The "Change in Dielectric Constant" column indicates the aforementioned change in dielectric constant. As mentioned above, the change in dielectric constant is the increase in dielectric constant corresponding to a 1-part increase in the amount of glass added. Figure 9 The information shown in the other columns is according to Figure 5 .

[0082] In Examples 30-34, the total amount of alkaline earth elements was varied. More specifically, in Example 30, the total amount of alkaline earth elements was set to 11 wt%. In Example 31, the total amount of alkaline earth elements was set to 19 wt%. In Example 32, the total amount of alkaline earth elements was set to 22 wt%. In Example 33, the total amount of alkaline earth elements was set to 25 wt%. In Example 34, the total amount of alkaline earth elements was set to 32 wt%.

[0083] In addition, although figures are omitted, the dielectric constants were measured when the glass addition amount was 12 parts by weight (hereinafter referred to as the first dielectric constant), 15 parts by weight (hereinafter referred to as the second dielectric constant), and 25 parts by weight (hereinafter referred to as the third dielectric constant). Based on the first, second, and third dielectric constants measured in Example 30, the dielectric constant change of Example 30 was derived. Based on the first, second, and third dielectric constants measured in Example 31, the dielectric constant change of Example 31 was derived. Based on the first, second, and third dielectric constants measured in Example 32, the dielectric constant change of Example 32 was derived. Based on the first, second, and third dielectric constants measured in Example 33, the dielectric constant change of Example 33 was derived. Based on the first, second, and third dielectric constants measured in Example 34, the dielectric constant change of Example 34 was derived.

[0084] The derived change in dielectric constant (in %) Figure 9 It is shown in the "Change in Dielectric Constant" column. Figure 9 It can be confirmed that the greater the increase in the stoichiometry of the alkaline earth group, the greater the change in dielectric constant. In other words, according to... Figure 9 It can be confirmed that the lower the concentration of alkaline earth elements, the lower the change in dielectric constant. Furthermore, it can be confirmed that if the concentration of alkaline earth elements is below 32 wt%, the change in dielectric constant can be suppressed to below 29.6%. It can be confirmed that if the concentration of alkaline earth elements is below 25 wt%, the change in dielectric constant can be suppressed to below 21.4%. It can be confirmed that if the concentration of alkaline earth elements is below 22 wt%, the change in dielectric constant can be suppressed to below 13.8%. It can also be confirmed that if the concentration of alkaline earth elements is below 19 wt%, the change in dielectric constant can be suppressed to below 2.7%. It can be confirmed that if the concentration of alkaline earth elements is below 11 wt%, the change in dielectric constant can be suppressed to below 1.2%.

[0085] Figure 10 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 10 Examples 35-37 and Comparative Example 19 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 10 Further details are shown in the middle.

[0086] exist Figure 10 The "First Principal Component," "Second Principal Component," and "Third Principal Component" columns represent the principal components. Figure 10The "Principal Component Ratio" column indicates the content of each compound that may be present in a principal component. More specifically, "1" in the "Principal Component Ratio" column indicates the content of the compound shown in the "First Principal Component" column. "2" in the "Principal Component Ratio" column indicates the content of the compound shown in the "Second Principal Component" column. "3" in the "Principal Component Ratio" column indicates the content of the compound shown in the "Third Principal Component" column. Figure 10 The information shown in the other columns is according to Figure 2 .

[0087] In Examples 35-37 and Comparative Example 19, the glass composition and glass addition amount were the same, but the ratio of the main components was different.

[0088] In Examples 35-37 and Comparative Example 19, the first main component was set as Mg2SiO4, and the second main component was set as BaTiO3. In Examples 35-37, the content of the second main component (BaTiO3) in the main components was controlled within the range of 3 mol% to 7 mol%. In contrast, in Comparative Example 19, the content of the second main component (BaTiO3) in the main components deviated from this range. More specifically, in Comparative Example 19, the content of the second main component (BaTiO3) in the main components was greater than 7 mol%. As a result, as Figure 10 As shown, in Examples 35-37, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all excellent. In particular, the absolute values ​​of the temperature characteristics in Examples 35-37 were smaller than the absolute values ​​of the temperature characteristics in Example 3, whose main component was Mg2SiO4. That is, the temperature characteristics of Examples 35-37 were better than those of Example 3. In contrast, in Comparative Example 19, the fQ value did not reach 15000.

[0089] Figure 11 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 11 Examples 38-43 and Comparative Example 20 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 11 Further details are shown in the middle. Figure 11 The table format is in accordance with Figure 10 .

[0090] In Examples 38-43 and Comparative Example 20, the first main component was set as Mg2SiO4, and the second main component was set as SrTiO3. In Examples 38-43, the content of the second main component (SrTiO3) in the main components was controlled within the range of 3 mol% to 13 mol%. In contrast, in Comparative Example 20, the content of the second main component (SrTiO3) in the main components deviated from this range. More specifically, in Comparative Example 20, the content of the second main component (SrTiO3) in the main components was greater than 13 mol%. As a result, as Figure 11 As shown, in Examples 38-43, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all good. In particular, the temperature characteristics of Examples 38-43 were the same as those of Examples 35-37, and better than those of Example 3. In contrast, in Comparative Example 20, the dielectric constant exceeded 9.0.

[0091] Figure 12 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 12 Examples 44-54 and Comparative Example 21 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 12 Further details are shown in the middle. Figure 12 The table format is in accordance with Figure 10 .

[0092] In Examples 44-51 and Comparative Example 21, the first main component was set as Mg2SiO4, and the second main component was set as CaTiO3. In Examples 44-51, the content of the second main component (CaTiO3) in the main components was controlled within the range of 3 mol% to 17 mol%. In contrast, in Comparative Example 21, the content of the second main component (CaTiO3) in the main components deviated from this range. More specifically, in Comparative Example 21, the content of the second main component (CaTiO3) in the main components was greater than 17 mol%. As a result, as Figure 12 As shown, in Examples 44-51, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all good. In particular, the temperature characteristics of Examples 44-51 were the same as those of Examples 35-37, and better than those of Example 3. In contrast, in Comparative Example 21, the dielectric constant exceeded 9.0.

[0093] In Examples 52-54, the first principal component was set as Mg2SiO4. Additionally, in Examples 52-54, two of the aforementioned BaTiO3, SrTiO3, and CaTiO3 were selected and included in the principal components (second principal component and third principal component). In Examples 52-54, the combinations of the selected principal components (second principal component and third principal component) were different. More specifically, in Example 52, the principal component consisted of Mg2SiO4, BaTiO3, and SrTiO3. In Example 53, the principal component consisted of Mg2SiO4, CaTiO3, and BaTiO3. In Example 54, the principal component consisted of Mg2SiO4, CaTiO3, and SrTiO3. The content of both the second and third principal components was 5 mol%. As a result, as... Figure 12 As shown, in Examples 52-54, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength are all excellent. In particular, the absolute values ​​of the temperature characteristics in Examples 52-54 are smaller than those in Examples 35-37, etc., and are therefore better.

[0094] according to Figures 10-12 It can be confirmed that the temperature characteristics are improved by not only containing Mg2SiO4 in the main component, but also further containing at least one of BaTiO3, SrTiO3, and CaTiO3 in the main component. Furthermore, according to... Figure 10 It can be confirmed that the BaTiO3 content is preferably below 7 mol%. According to... Figure 11 It can be confirmed that the SrTiO3 content is preferably below 13 mol%. According to... Figure 12 It can be confirmed that the content of CaTiO3 is preferably below 17 mol%.

[0095] Figure 13 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Figure 13 Examples 55-57 and Comparative Example 22 are shown. Additionally, for comparison, Figure 2 The embodiment 3 shown in the text is as follows: Figure 13 Further details are shown in the middle.

[0096] exist Figure 13 The “CuO content” column indicates the CuO content (parts by weight) relative to 100 parts by weight of the main component. Figure 13 The information shown in the other columns is according to Figure 2 .

[0097] In Examples 55-57 and Comparative Example 22, the composition of the main components was the same. Furthermore, in Examples 55-57 and Comparative Example 22, the composition of the glass components was the same. Furthermore, in Examples 55-57 and Comparative Example 22, the amount of glass added was the same. In Examples 55-57 and Comparative Example 22, the content of the copper compound was different. In Examples 55-57, the content of the copper compound was controlled within a range of more than 0 parts by weight and less than 7 parts by weight. In contrast, in Comparative Example 22, the content of the copper compound deviated from this range. More specifically, in Comparative Example 22, the content of the copper compound was set to 7 parts by weight. As a result, as... Figure 13 As shown, in Examples 55-57, the sintering temperature, dielectric constant, fQ value, temperature characteristics, and strength were all excellent. In particular, the sintering temperatures of Examples 55-57 were lower than the sintering temperature of Example 3, which did not contain the copper compound. That is, the sintering temperatures of Examples 55-57 were better than those of Example 3. In contrast, in Comparative Example 22, the fQ value did not reach 15000.

[0098] according to Figure 13 It has been confirmed that the sintering temperature is improved by including copper oxide (a copper compound) in the dielectric ceramic composition. Furthermore, it has been confirmed that a good dielectric ceramic composition can be obtained if the copper oxide content is less than 7 parts by weight per 100 parts by weight of the main component.

[0099] Figure 14 , Figure 15 This is a table used to compare the experimental results of multiple embodiments with the experimental results of multiple comparative examples. Examples 58-60 and Comparative Examples 23 and 24 are... Figure 14 , Figure 15 It is shown in the middle. Additionally, for comparison, Figure 2 The embodiment 1 shown in the figure is Figure 14 , Figure 15 Further details are shown in the middle.

[0100] In Examples 1, 58-60, and Comparative Examples 23 and 24, the composition of the main components was the same. On the other hand, in Examples 1, 58-60, and Comparative Examples 23 and 24, the amount of glass component added was different. More specifically, in Examples 1, 58-60, and Comparative Examples 23 and 24, the amount of first glass component added as a first glass component and the amount of second glass component added as a second glass component were different. The composition of the first glass component and the composition of the second glass component were different. Figure 2 The glass shown has the same composition. Figure 14 , Figure 15 The diagram shows the second glass composition as a second glass component. For example... Figure 14 , Figure 15As shown, a boron-based glass containing SiO2, BaO, B2O3, and ZnO was prepared as the second glass composition. In Examples 1, 58-60, the amount of the second glass added was controlled within a range of 0 parts by weight or more and 3 parts by weight or less. In contrast, in Comparative Examples 23 and 24, the amount of the second glass added deviated from this range. More specifically, in Comparative Examples 23 and 24, the amount of the second glass added was set to 4 parts by weight or more. As a result, as Figure 14 , Figure 15 As shown, in Examples 1 and 58-60, the sintering temperature, dielectric constant, fQ value, temperature characteristics, strength, and acid resistance were all excellent. Particularly regarding acid resistance, as... Figure 15 As shown, the erosion distance in Examples 1, 58-60 was less than 3 μm, which is considered standard. In contrast, the erosion distance in Comparative Examples 23 and 24 was 4 μm or more.

[0101] according to Figure 14 , Figure 15 (in particular Figure 15 It can be confirmed that by suppressing the content of boron-based glass in the dielectric ceramic composition to less than 3 parts by weight, the dielectric ceramic composition can be endowed with good acid resistance.

[0102] The following notes are also disclosed in relation to the above-described implementation methods and embodiments.

[0103] (Note 1) The dielectric ceramic composition disclosed herein is a dielectric ceramic composition containing magnesium olivine as a main component and glass as a secondary component, wherein the glass component comprises lithium, calcium, barium and silicon, and more than 12 parts by weight of the glass component are added relative to 100 parts by weight of the main component.

[0104] (Note 2) Alternatively, it may be the dielectric ceramic composition described in Appendix 1, wherein the amount of glass component added is 25 parts by weight or less relative to 100 parts by weight of the main component.

[0105] (Note 3) Alternatively, it may be the dielectric ceramic composition described in Appendix 1, wherein the content of lithium oxide in the glass component is 6 wt% or more and 18 wt% or less, the content of calcium oxide in the glass component is 2 wt% or more and 9 wt% or less, the content of barium oxide in the glass component is 6 wt% or more and 20 wt% or less, and the content of silicon dioxide in the glass component is 50 wt% or more and 75 wt% or less.

[0106] (Note 4) Alternatively, it may be the dielectric ceramic composition described in Appendix 3, wherein the content of alkaline earth elements in the glass component, i.e., the total amount of alkaline earth elements, is less than 32 wt%.

[0107] (Note 5) Alternatively, it may be the dielectric ceramic composition described in Appendix 4, wherein the alkaline earth group composition is 25 wt% or less.

[0108] (Note 6) Alternatively, it may be the dielectric ceramic composition described in Appendix 5, wherein the amount of the alkaline earth group is less than 22 wt%.

[0109] (Note 7) Alternatively, it may be the dielectric ceramic composition described in Appendix 6, wherein the alkaline earth group composition is 19 wt% or less.

[0110] (Note 8) It may also be a dielectric ceramic composition according to any one of Appendices 1 to 7, wherein the main component further comprises at least one of barium titanate, strontium titanate and calcium titanate, wherein the content of barium titanate in the main component is 7 mol% or less, the content of strontium titanate in the main component is 13 mol% or less, and the content of calcium titanate in the main component is 17 mol% or less.

[0111] (Note 9) It may also be a dielectric ceramic composition according to any one of Appendices 1 to 7, wherein, relative to the main component, it contains a copper compound of greater than 0 parts by weight and less than 7 parts by weight converted from copper oxide.

[0112] (Postscript 10) The molded body (16) disclosed herein is a molded body having a dielectric ceramic composition according to any one of Appendices 1 to 7.

[0113] (Postscript 11) It may also be the molded body described in Note 10, which is a sintered molded body with a relative permittivity of 9.0 or less, a Q value of fQ (the product of Q value and resonant frequency) of 15000 or more, and a three-point bending strength of 270 MPa or more.

[0114] (Postscript 12) It may also be the molded body described in Note 11, wherein the relative permittivity is 8.5 or less.

[0115] (Postscript 13) The electronic component (10) disclosed herein is an electronic component having the molded body described in Appendix 10.

[0116] (Postscript 14) It could also be the electronic component described in Note 13, wherein a silver-containing conductor (12) is integrally fired with the molded body.

[0117] It should be noted that the present invention is not limited to the above disclosure, and various configurations may be adopted without departing from the spirit of this disclosure.

Claims

1. A dielectric ceramic composition comprising magnesium olivine as a main component and glass as a secondary component, wherein, The glass composition includes lithium, calcium, barium, and silicon. The glass component was added at least 12 parts by weight relative to 100 parts by weight of the main component.

2. The dielectric ceramic composition according to claim 1, wherein, The amount of glass component added is less than 25 parts by weight relative to 100 parts by weight of the main component.

3. The dielectric ceramic composition according to claim 1, wherein, The lithium oxide content in the glass composition is 6 wt% or more and 18 wt% or less. The calcium oxide content in the glass composition is above 2 wt% and below 9 wt%. The barium oxide content in the glass composition is above 6 wt% and below 20 wt%. The silica content in the glass composition is above 50 wt% and below 75 wt%.

4. The dielectric ceramic composition according to claim 3, wherein, The content of alkaline earth elements in the glass composition, i.e., the total amount of alkaline earth elements, is less than 32 wt%.

5. The dielectric ceramic composition according to claim 4, wherein, The total amount of alkaline earth elements is below 25 wt%.

6. The dielectric ceramic composition according to claim 5, wherein, The total amount of alkaline earth elements is below 22 wt%.

7. The dielectric ceramic composition according to claim 6, wherein, The total content of the alkaline earth group is below 19 wt%.

8. The dielectric ceramic composition according to any one of claims 1 to 7, wherein, The main component also includes at least one of barium titanate, strontium titanate, and calcium titanate. The content of barium titanate in the main component is less than 7 mol%. The content of strontium titanate in the main component is less than 13 mol%. The content of calcium titanate in the main component is less than 17 mol%.

9. The dielectric ceramic composition according to any one of claims 1 to 7, wherein, Relative to the main component, it contains a copper compound that is greater than 0 parts by weight and less than 7 parts by weight when converted from copper oxide.

10. A molded body having a dielectric ceramic composition according to any one of claims 1 to 7.

11. The molded body according to claim 10 is a sintered molded body having a relative permittivity of 9.0 or less, a Q value equal to or greater than the product of the Q value and the resonant frequency (fQ value), and a three-point bending strength of 270 MPa or more.

12. The molded article according to claim 11, wherein, The relative permittivity is 8.5 or less.

13. An electronic component having a molded body according to claim 10.

14. The electronic component according to claim 13, wherein, The silver-containing conductor is integrally fired with the molded body.

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